Lightweight and low-cost one-dimensional carbon materials, especially biomass carbon fibers with multiple porous structures, have received wide attention in the field of electromagnetic wave absorption. In this paper, graphene-coated N-doped porous carbon nanofibers (PCNF) with excellent wave absorption properties were successfully synthesized via electrostatic spinning, electrostatic self-assembly, and high-temperature carbonization. The obtained results showed that the minimum reflection loss of the absorbing carbon fiber obtained under the carbonization condition of 800 °C is -51.047 dB, and the absorption bandwidth of reflection loss below -20 dB is 10.16 GHz. This work shows that carbonization temperature and filler content have a certain effect on the wave-absorbing properties of fiber, graphene with nanofiber, and the design and preparation of high-performance absorbing materials by combining the characteristics of graphene and nanofibers and multi-component coupling to provide new ideas for the research of absorbing materials.